Process of preparing derivatives of petroleum hydrocarbon acid sludge



Patented Nov. 10, 1942 2,301,335

UNITED STATES PATENT OFFICE PROCESS OF PREPARING DERIVATIVES OFPETROLEUM HYDROCARBON ACID SLUDGEv Jere C. Showalter, Goose Creek, andMehemet Wiggen, Baytown, Tex., assignors to Standard Oil DevelopmentCompany, a corporation of Delaware No Drawing. Application September 1,1939, Serial No. 293,050

Claims. (Cl. 196-148) centage of drying oil distillate varies from 30 to4'7 per cent based on the oil separated from cracked naphtha acidsludge.

The drying oil distillate and the resin separately (the latter innaphtha solution) are treated ,with 50 and 100 pounds of equivalent 98%sulfuric acid per barrel, respectively, at approximately 80 to 90 F.After separating the resulfuric acid. 5

It is well known that hydrocarbon oil acid sulting secondary sludges,the drying oil and the sludges that are separated from the hydrocarbonnaphtha solution of the resin are contacted sepaoils contain substantialamounts of hydrocarbons rately with a deoolorizing clay, such as fullerstogether with the spent sulfuric acid. These hyearth, Milwhite No. 2clay, Super Filtrol, etc. drocarbon oil acid sludges, on dilution withwater In the case of the drying oil, the clay contacting and maintainingat an elevated temperature, step is carried out with approximately onepound separate into two layers, one a dilute acid layer of clay pergallon at about 300 F. for a short and the other an oil layer. This oillayer has period of time ranging up to about 30 minutes.- been furtherpurified by neutralization and frac- After separation of the clay byfiltration, the drytionation to produce hydrocarbon oils which may ingoil can then be used as such or with the addibe used as drying oils. Theobjection to this tion of a drier, such as lead or manganese naphprocessis that the hydrocarbon oil thus prepared thenate or oleate, etc.- Thenaphtha solution of is a dark, discolored oil and even though it isresin is contacted with about 2 pounds of clay treated with adecolorizing clay, the oil is not per gallon of resin (naphtha-freebasis), at atmossuitable for use in paints due to its dark color pherictemperature for approximately 30 minutes. and incompatibility with leaddriers. The filtered resin solution is then subjected to An object ofthis invention is to prepare from distillation to remove the naphtha. Itmay somehydrocarbon oil acid sludges a drying oil and a timesbedesirableto treat the acid-treated drying resin which may be used inlight colored paintsv oil and acid-treated resin with propane beforeand/or varnishes. clay treating. The light-colored finished resinAccording to the preferred embodiment of this may be used in varnishmanufacture. invention, a cracked naphtha or a hydrocarbon When amaximum yield of drying oil is desired, naphtha that contains a largepercentage of unthe original naphtha sludge must be hydrolyzed saturatedhydrocarbons is treated with strong suland neutralized preferably withinone or two furic acid. After the mixture of acid and cracked hours afterthe formation of the sludge from the naphtha is agitated for asufiicient time to comnaphtha. If the sludge is allowed to remain inplete the reaction of sulfuric acid on the unsatuthe acid state for arelatively long period of time, rated or other highly reactiveconstituents of the the drying oil tends to polymerize and form acracked naphtha, it is allowed to settle and the larger yield of resinthan in the above-mentioned acid sludge layer separates to the bottomand is instance. When a maximum yield of resin is the withdrawn from thetreated naphtha. This acid desired product, on the other hand, theoriginal sludge is mixed with suflicient water to hydrolyze naphthasludge is allowed to remain inthe unthe esters and is allowed to settleinto two layers hydrolyzed state for a relatively long period of and thebottom layer of mineral acid is removed. time.

The upper or oily layer is then neutralized by 40 If the hydrolyzedsludge containing small perwashing with an aqueous solution of sodiumcarcentages of free mineral acid is permitted to rebonate or otheralkali. .The washed oil is then main in contact with this free acid fora relatively pgxed with 4 to 5 volumes of propane or other long periodof time, a tendency for the drying oil liquefied saturated hydrocarboncompounds that to polymerize to resin persists. Consequently, if arenormally gaseous at. ordinary. temperature for the free acid is notremoved by other means which each volume of the oil and maintained at atemwill be described later, it is preferred to neutralize perature of120 F. for about 30 minutes. A the hydrolyzed oily layer promptly withaquelayer of carbonaceous material settles out and is ous sodiumcarbonate or other alkali in order to removed. After removal of thepropane by vaporcheck further polymerization. However, this neuization,the decarbonized oil is subjected to firet'ralization step introducesundesirable salts which and-steam or vacuum distillation and anovercannot be removed by simple water washing due head fraction boilingbetween about 520 and to severe emulsion difficulties. Nevertheless, if650 F. at normal atmospheric pressure is rethese salts are not removedprior to the distillacovered as a crude drying oil. A residue of resintion step, they decompose and release sulfur combottoms is withdrawnfrom the still. The perpounds which are corrosive to the distillationequipment and result in the production of drying oils which areincompatible with lead driers:

The objectionable salts and some carbonaceous or asphaltic material canbe readily precipitated and removed by'dissolving the neutralized oilylayer in 4 to 5 volumes fied normally gaseous hydrocarbon atapproximately 120 F. If it is convenient to propane treat the hydrolyzedoily layer immediately, the neutralization step may be omitted. Sincepropane treatment precipitates the traces of free mineral acid andacidic esters along with the carbonaceous material, polymerizationof thecrude drying oil is effectively checked and subsequent distillation andrefining may be delayed.

Whereas considerable quantities of free sulfur begin to be liberated atabout 320 F. when distilling non-propane treated, hydrolyzed orneutralized sludge, no harmful quantity of free sulfur or sulfur dioxideis observed during the distillation' of propane treated oil.

Although it is preferred to separate during distillation a lightfraction boiling below about 520 F. in order that the finished dryingoil may conform to certain specifications for commercial drying oils,portions of the lower boiling fraction which also have drying andthinning properties may be includedin the finished drying oil.

The crude drying oil distillate is preferably refined by treating itwith about 50 pounds of equivalent 98% sulfuric acid per barrel of oiland, after separating the resulting secondary sludge, to contact theacid oil with about one pound of clay per gallon of oil at a temperatureof approximately 300 F., in conventional manner. It was found, however,that quantities as low as pounds of acid per barrel can be used toproduce a finished oil of desirable color provided the clay dosage isappreciably increased. An oil of desirable color quality cannot beproduced economically by simple clay treatment in the absence of a prioracid treat. Variation of the acid treat between the above-mentionedlimits does not adversely affect the drying properties of the oil. Thecombined drying oil and resin fractions may be acid and clay treated,although the yield of resin is lowered and the color of the drying oilfraction is appreciably decreased over those obtained in the preferredprocedure.

It has been shown in the prior art that resins prepared from sludgesobtained in the aluminum chloride treatment of cracked naphthas or otherhighly unsaturated hydrocarbon fractions may be refined by fluxing witha light non-aromatic hydrocarbon fraction and contacting with anactivated clay at temperatures in the range of about 200 to 450 F. forshort periods of time, on the order of 5 to 10 minutes. This treatmentproduces some improvement in color of the resins obtained from sulfuricacid sludges of cracked naphthas, but it does not yield as light coloredproduct as does that prepared by this preferred process of removingcarbonaceous and acidic material by propane precipitation, said treatingin two volumes of naphtha with about 100 pounds of acid per barrel(unfluxed basis), and contacting with about two pounds of activated ornon-activated clay per'gallon (unfluxed basis) at room temperature whilestill in naphtha solution. The following examples clearly illustrate theresults of these treatments:

EXAMPLE 1 Cracked naphtha acid sludge was hydrolyzed with water and theoily layer was neutralized with sodium carbonate. After aging this crudematerial for 16 days, it was decarbonized in four volumes of propane at120 F., and the demoof propane or other liquepanized oil wasfire-and-steam distilled to a 23.2% resinbottoms. The crude resin had anabsolute color of 5040.

EXAMPLE 2 'Exnn'm: 3

One hundred grams of the crude resin prepared in Example 1 were crushedand mixed with 100 grams of Super Filtrolclay. After heating the mixtureto 450 2F. and stirring for 5 minutes,

it was cooled and fluxed with 500 cc. of non-' "aromatic naphtha so thatthe clay could be separated by filtration. The stripped resin had anabsolute color of 1370.

Exmru: 4

for 30 minutes with two pounds of Milwhite No. 2

(non-activated) clay per gallon based on the unfluxed acid treatedresin. The filtered and stripped product had an absolute color of 584.

In the foregoing examples the absolute color of the resin was determinedby dissolving a one gram sample of the filtered and naphtha-free,finished resin in a measured volume of water white naphtha sufficient toyield a Robinson color between 9 and 12. The observed color was obtainedin a standard Tag-Robinson colorimeter by matching the sample against aNo. 2 color disc and reading the scale within the nearest millimeter.This observed color was then converted to absolute units and the latterwere multiplied by the number of cubic centimeters of naphtha used fordilution. Conversions of Robinson color to absolute color were obtainedfrom a graph wherein the following are specific points:

Robinson Absolute color color EXAMPLE 5 tillate and the crude resinbottoms (the latter in naphtha solution) were subsequently treated withacid and clay for improvement in color. In

case B of Table I, a sample of the acid sludge was hydrolyzed and thedecanted oily layer waswater washed but not neutralized. The resultanthydrolyzed sludge oil was decarbonized by treating with liquid propane.After separating the precipitated asphaltic material and flashing offthe propane, the decarbonized oil was fire-andsteam distilled into aheavy naphtha cut, a drying oil distillate and a crude resin bottoms.This drying oil distillate and crude resin bottoms were subjected toacid and clay treatment just as in case A. The finished drying oil andresin of case B are sufliciently light in color to be used in thepreparation of light-colored paints and/or lightcolored varnishes,whereas the products of case A are too dark in color for such usage.

activated clay. Both products were light in color, the drying oil beingsatisfactory for use in the preparation-of light-colored paints andvarnishes, and the resin being satisfactory for use in the preparationof light-colored varnishes.

Case B illustrates the impossibility of producing economically alight-colored drying oil without acid treating the crude product. Thetreating procedure employed in this case. differs from that of case Aonly in the respect that no acid was used on the crude drying oildistillate; instead, an excessively large clay treat was'employed in anunsuccessful attempt to decolorize satisfactorily the distillate.

Case C illustrates the type of products obtainable from a hydrolyzedcracked naphtha acid sludge oil which had been neutralized and agedseveral days before subjecting it to propane, acid and clay treatment inaccordance with the procedure of case A. In this particular example,

- the hydrolyzed acid sludge oil was neutralized Table I Cracked naphthaacid sludge Case A Case B soda neupropane tralized treated Treatingconditions for acid sludge:

Temperature of hydrolysis, F 160 170 Hydrolyzing ratio, sludge to water1:1 11 Treating conditions for hydrolyzed sludge oil:

Water washing ratio, sludge oil to Water... 1:1 1:1 Beds forneutralization None Declarbonization ratio, propane to sludge 4 l oDecarbonization temperature, F 120 Yield of neutralized or decarboni percent hydro. sludge o1 l 79.4 Atmospheric steam distillation of treatedsludge oil:

Still temperature for naphthacut, F.. 320-420 220-555 Still temperaturefor drying oil cut, F- 420-650 555-650 Yield of naphtha, vol. per cent24.3 28.4 Yield of drying oil distillate, vol. per cent. 51,3 47,8 Yieldof resin bottoms, vol. per cent 23,9 23,8 Treatment, yields and qualityof drying oil:

Lbs. 98% H 80 per Bbl. drying oil distlllate" 59.4 50 Acid treat gtemperature, F 30-90 80-90 Yield of acid treated drying 0 centhydrolyzed sludge oil. 37.7 27.6 Lbs non-activated clay per g 1.0 1.0Temperature of contact, F. 300 300 Time of contact, minutes. 30 30 Yieldof clay contacted oil, vol. per cent hydrolyzed sludge oil 33.9 26.5Gravity, A. P. I. 16.0 17.7 Flash, "F 285 250 Viscosity at 100 F.,Saybolt Un versal.... 345 187 Viscosity at 210 F., Saybolt Universal.45.7 40.4 Color, Robinson 4 7% Saponification number 1.54 1.6 Acidnumber (neutralization valu 0.25 0.14 Iodine numbe 208 293 Carbonresidue, per cent 0.4 0.22 Sulfur, per cen 1.2 1.3 Drying time, ho

sunlight 4 6 Treatment, yields and quality of resin bottoms:

Fluxing ratio, resin: naphtha 1: 2 1:2 Lbs. 98 per cent H 80 per bbi.resin (uniluxed basis) 100 100 Lbs. non-activated clay per gallon resin(unfluxed basis) 1.5 2.0 Temperature of contact, F 85 85 Time ofcontact, minutes 30 30 Yield of clay-contacted, naphthavol. per centhydrolyzed sludge 011 20.0 11.6 S clflc gravity 0.991 A solute color2740 786 Ring-and-ball softening pc 175 186 furic acid and subsequentlycontacted with nonwith sodium carbonate and allowed to age 16 days priorto completion'of the treatment for converting it into a drying oil and aresin.

Table II Freshly hydrolyzed cracked Charge stock naph. acid sludgeCondition when propane Case A Case B Case 0 decarbonized Unneu- Unneu-Neutralized tralized tralized Ratio, pro ane: Hydrolyzed sludge. 4:1 4:14:1 Decarbon zingbtei iperature, F 120 120 120 Yield of decaionized oil,per cent. 79. 4 79. 4 87. 0 Atmoiixphertic steam still temp., F nap cu220-555 220-520 220-520 Atmospheric steam still temp., F.

, drying oil out 555-650 520-650 520-650 Yield of naphtha, per cent. 22.5 23. 5 25.0 Yield of drying oil distill cent 0 38. 0 36. 4 41. 8 Yieldof resin bottoms, per cent- 18.9 19. 5 20. 2 Treatment, yields andquality of drying 011:

Lbs. 98% sulfuric acidlbbl.

drying oil distillate 50 0 50 Yield of acid treated drying oil,

er cent... 32.0 32.5 L s. non-activated clay/gal.

acid 011 1.0 2.0 1.0 Contacting temperature, F 300 300 300 Time ofcontact, minutes 30 30 7 Yield of clay contacted oil cent 30. 8 34. 231. 2 Gravity, A 17. 7 l7. 7 l7. 1 Flash, 250 260 260 Saybolt V seconds.187 214 329 Saybolt Viscosity at 210 F seconds 40. 4 41. 5' 44. 5 Color,Robinson I 7% 1% 9+ Saponification number. l. 6 0. 84 0. 84 Acid number(neut. value). 0. 14 0.2 0.14 Iodine number 293 325 299 Carbon residue,per cent- 0.22 0. 38 0. 29 Sulfur, per cent 1. 3 l. 5 l. 3 Drying timehours exposed direct sunl gh 6 6 6 Treatment, yields resin bottoms:

Ratio, crude resin: Naphtlia flux 1:2 1:2 1:2

Lbs. 98% sulfuric acid/bbl.

resin (unfluxed) 100 100 100 Yield of acid treated resin (uniiuxed), percent l4. 0 l4. 0 l4. 8 Lbs. non-activated clay/gal.

resin miiuxed) 2.0 2.0 2.0 Contacting temperature, F--. 85 85 85 T me ofcontact, minutes 30 30 Yield of clay contacted, naphtha-free resin, percent 13. 2 13.2 13.9 Specific gravity. 0. 991 0. 991 0. 985 Absolutecolor- 786 786 584 Rin qu d-b NorE.-All yields calculated on basis ofwater and acid-free hydrolyzed sludge.

While a specific object of this invention is to prepare from hydrocarbonoil acid sludge a drying oil and a resin which may be used inlightcolored paints and/or light-colored varnishes, it is distinctlyunderstood that these products possess properties which makethemadaptable for a wide variety of other uses, such as those hereinaftermentioned.

The drying oil may be used in the preparation of paints and varnishes ofall kinds, adhesives, putties, printing inks, and waterproofingcompounds for brick, tile, stucco, or concrete buildings. Itrmay also beused for waterproofing fabrics, for an adhesive in briquetting, and as asubstitute in certain instances for natural drying or semi-drying oils.

The resin may be used in pigmented tiles, floor covering, roofingmaterial, panel boards, moulding powders, and waterproofing compoundsfor brick, tile, stucco, or concrete walls or floors; furthermore, itmay be used in almost all lacquers, varnishes, paints and alliedmaterials. The resin may be used also for electrical insulation, forsizing fabric or paper, as a protective covering for pipe lines, and asan impregnant for improving the appearance, strength and waterproofingqualities of cardboard, fibre board, or wood. In the unrefined state,resins obtained from hydrolyzed cracked naphtha acid sludge oil areparticularly well adapted for use in the manufacture of clay pigeons;for example, the resins are compounded with spent contact clay which hasbeen used in decolorizing oil and from which the excess oil has beenremoved.

We claim:

1. A process of preparing derivatives of petroleum hydrocarbon acidsludge which comprises the following combination of steps treating withwater the sulfuric acid sludge obtained by treating cracked hydrocarbonnaphthas with sulfuric acid, separating an acid-water solution, treatingthe residual material with propane, settling, separating a layer of thecarbonaceous material that settles out, distilling the residual materialto remove propane, treating the residual material with sulfuric acid,separating the sulfuric acid and clay treating the residual material,filtering to remove the clay and fractionating the residual materialinto an oil fraction and a fraction that is solid at ordinarytemperatures.

2. A process of preparing derivatives of an acid sludge which comprisesthe following combination of steps treating with water an acid sludgeobtained by contacting cracked hydrocarbon naphthas with sulfuric acid,removing the aqueous acid solution, treating the oily layers with 4 to 5volumes of propane for each volume of oil, settling, separating aprecipitate formed thereby, distilling to separate the volatilehydrocarbons and a fraction boiling between about 520 and 650 F. and aresidual fraction, and

treating the said two fractions separately with sulfuric acid and clay.

3. A process of preparing derivatives of an acid sludge which comprisesthe following combination of steps treating with water an acid sludgeobtained by contacting cracked hydrocarbon naphthas with sulfuric acid,removing the aqueous acid solution, treating the oily fraction with 4 to5 volumes of propane for each volume of oil, settling, separating aprecipitate formed thereby, distilling to separate the volatilehydrocarbons boiling below 520 F. and a fraction boiling between about520 and 650 F., treating said fraction with sulfuric acid, settling,separating the sulfuric acid sludge, contacting the residual fractionwith a decolorizing clay, and separating the decolorizing clay byfiltration.

4. A process of preparing derivatives of an acid sludge which comprisesthe following combination of steps treating at a temperature from F. toF. with water an acid sludge obtained by contacting cracked hydrocarbonnaphthas with sulfuric acid, removing the aqueous acid solution,treating the oily fraction with 4 to 5 volumes of propane for eachvolume of oil, settling, separating the precipitate formed thereby,distilling to separate the volatile hydrocarbons and a fraction boilingbetween about 520 and 650 F., treating the said fraction with 50 poundsof 98% sulfuric acid per barrel of oil, settling, separating a secondarysludge, contacting the acid-oil fraction with 1 pound of clay per gallonof oil at a temperature of approximately 300 F. and filtering toseparate the clay.

5. A process of preparing derivatives of petroleum oil whichcomprises'the following combination of steps, treating crackedhydrocarbon naphthas with sulfuric acid, separating an acid sludgethereby formed, mixing the separated sludge with water, settling to formtwo layers, an aqueous layer and-an oil layer, removing the aqueouslayer, neutralizing the oil layer with an aqueous alkali solution,settling, separating a top oil layer, treating the separated oil layerwith a liquefied normally gaseous saturated hydrocarbon, settling,separating a layer of carbonaceous material, subjecting the residualmaterial to distillation to separate any material boiling below about520 F., contacting the residual material with sulfuric acid, settling,separating the sulfuric acid layer, contacting the residual materialwith a decolorizing clay, filtering to separate the clay and subjectingthe filtrate to distillation to obtain a fraction boiling between about520 to 650 F. and a residual normally solid material.

JERE C. SHOWALTER. MEHEMET WIGGEN.

